Organic peroxide



Patented May 1, 1945 Franklin Strain, Barberton. Ohio, assignor to Pittsburgh Plate Glass Company, Pittsburgh, Pa., a corporation oi Pennsylvania No Drawing. Application March 21, 1944,

Serial No. 527,487

Claims. (Cl. 260-463) V This application relates to anew class of peroxy compounds and methods for preparing them. The new compounds are alkyl carbonates wherein one oi the alkyl groups is separated from the carbonate radical by a peroxy Oxy en atom.

One of the purposes of the invention is to provide a new group of liquid peroxide compounds for use as polymerization catalysts. A further purpose is to provide liquid percarbonate compounds which are stable to heat and percussion,

thereby eliminating the danger oi explosion during use.

This new group of compounds has the structuralformulaas follows: I 1

. R.-0-o'-o-0 Ri wherein R1 and R: are alkyl radicals. The groups R1 and R2 may be the same or difierent alkyl radicals. V

The new compounds ar prepared by reactin an alkyl hydroperoxide with an alkyl chloroformate in the presence of a basic agent such as pyridine or an oxide or hydroxide of 'an alkaline metal. The reaction is preferably conducted in the presence or sodium hydroxide and at a temperature below about C. The alkyl hydroperoxide and the alkyl chloroformate are each cooled separately and then combined. The sodium hydroxide is then added gradually at a rate sufficient to enable the maintenance or thereaction temperature below a prescribed maximum,

- usually less than C. An ice bathis necessary to dissipate the heat of reaction and rapid stirring is desirable to Prevent local excesse in temperature and the incident losses of yield. After the reactants have been combined the mixture should be stirred for about 15 minutes to insure completion oi the reaction. The liquid peroxide compound separates from the aqueous liquor on standing. It is removed and subsequently washed and dried. The new group of compounds are colorless liquids which are very stable to heat and percussion, most or them bein capable of distillation. They areeflective polymerization catalysts for .ethylenic compounds. They are useful in bleaching operations and other oxidation reactions.

Further details of the preparation and use of the new peroxy compounds are set forth in the.

liquid peroxy carbonate was distilled at 63 C.

and 2 to 3 mm. pressure. A colorless liquid comlow 3 C. The reaction vessel was submerged in a bath containing a mixture of salt and ice. Atter the reagents had been combined, the stirringwas continued for 20 minutes. The two liquid phases of the reaction mixture were then separated. The nonaqueous portion was washed with dilute hydrochloric acid and with waterand then dried over anhydrous sodium sulfate. The

pound was thereby obtained.

A 10 g. sample of diallyl phthalate was mixed' with 0.4 g. of t-butylperoxy isopropyl carbonate and heated for 5 hours at 90 C. A hard colorless resin was thereby formed,

Example 11 slowly at a rate sumcient to prevent the increase in temperature to above 0 C. When the reagents were entirely combined cc. oi. ether were added. The nonaqueous layer containing ether and percarbonate was separated and washed with dilute hydrochloric acid and water until neutral. The ether and percarbonate were separated from each other by distillation.

A 10 g. sample oi. ethylene glycol bis (allyl car- 'bonate) was mixed with 0.5 g. of ethylperoxyethyl carbonate and heated at C. for 72 hours. A hard transparent polymer was formed.

Although the invention has been described with .respect to certain specific embodiments it is not,

intended that the details thereof should be construed as limitations upon the scope of the invention. 4

I claim: 1. A compound having the molecular structure:

' in which R1 and Rs are alkyl radicals.

2. As a new compound t-butylperoxy isopropyl carbonate.

3.Ae a new compound ethylperoxy isopropyl carbonate. Y 4. As a new compound ethylperoxy ethyl per-' carbonate;

5. A method of preparing an alkylperoxy alkyl carbonate which comprises reacting an alkyl hydroperoxide and an alkyl chloroiormate in the presence or an alkaline reagent at a temperature sodium hydroxide was added slowly at a rate sub fiicient to maintain the reaction temperature bebelow20 C. 

